JP5969169B2 - Composite separation membrane - Google Patents
Composite separation membrane Download PDFInfo
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- JP5969169B2 JP5969169B2 JP2011042707A JP2011042707A JP5969169B2 JP 5969169 B2 JP5969169 B2 JP 5969169B2 JP 2011042707 A JP2011042707 A JP 2011042707A JP 2011042707 A JP2011042707 A JP 2011042707A JP 5969169 B2 JP5969169 B2 JP 5969169B2
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- polymer
- membrane
- gas
- amine compound
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- 239000012528 membrane Substances 0.000 title claims description 81
- 238000000926 separation method Methods 0.000 title claims description 62
- 239000002131 composite material Substances 0.000 title claims description 42
- -1 amine compound Chemical class 0.000 claims description 110
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 76
- 230000002209 hydrophobic effect Effects 0.000 claims description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000001569 carbon dioxide Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920005597 polymer membrane Polymers 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 9
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 239000012466 permeate Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 description 75
- 239000000243 solution Substances 0.000 description 32
- 239000000178 monomer Substances 0.000 description 31
- 239000002904 solvent Substances 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 20
- 239000000412 dendrimer Substances 0.000 description 20
- 229920000736 dendritic polymer Polymers 0.000 description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 229920006254 polymer film Polymers 0.000 description 19
- 229920000962 poly(amidoamine) Polymers 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003431 cross linking reagent Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000012719 thermal polymerization Methods 0.000 description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 11
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 description 11
- 125000004430 oxygen atom Chemical group O* 0.000 description 11
- 125000004434 sulfur atom Chemical group 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 125000004492 methyl ester group Chemical group 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 229920001600 hydrophobic polymer Polymers 0.000 description 8
- 229920002492 poly(sulfone) Polymers 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 239000004831 Hot glue Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000003100 immobilizing effect Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical group C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- UROHSXQUJQQUOO-UHFFFAOYSA-M (4-benzoylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C1=CC(C[N+](C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 UROHSXQUJQQUOO-UHFFFAOYSA-M 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
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- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- LHYVEOGDJNQNEW-UHFFFAOYSA-N 1-amino-2-methylbutan-2-ol Chemical compound CCC(C)(O)CN LHYVEOGDJNQNEW-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
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- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- ZMLXKXHICXTSDM-UHFFFAOYSA-N n-[1,2-dihydroxy-2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NC(O)C(O)NC(=O)C=C ZMLXKXHICXTSDM-UHFFFAOYSA-N 0.000 description 1
- AYGYHGXUJBFUJU-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCNC(=O)C=C AYGYHGXUJBFUJU-UHFFFAOYSA-N 0.000 description 1
- IGXGJIVGBCOERN-UHFFFAOYSA-N n-[5-ethyl-3-(2-methylprop-2-enoylamino)-6-phenylphenanthridin-5-ium-8-yl]-2-methylprop-2-enamide;bromide Chemical compound [Br-].C12=CC(NC(=O)C(C)=C)=CC=C2C2=CC=C(NC(=O)C(C)=C)C=C2[N+](CC)=C1C1=CC=CC=C1 IGXGJIVGBCOERN-UHFFFAOYSA-N 0.000 description 1
- VVSGFSHAUFPBFM-UHFFFAOYSA-N n-[5-ethyl-6-phenyl-3-(prop-2-enoylamino)phenanthridin-5-ium-8-yl]prop-2-enamide;bromide Chemical compound [Br-].C12=CC(NC(=O)C=C)=CC=C2C2=CC=C(NC(=O)C=C)C=C2[N+](CC)=C1C1=CC=CC=C1 VVSGFSHAUFPBFM-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Description
本発明は、二酸化炭素を含有する混合ガスから二酸化炭素を分離するための複合分離膜および該複合分離膜を用いた二酸化炭素の分離方法に関する。 The present invention relates to a composite separation membrane for separating carbon dioxide from a mixed gas containing carbon dioxide and a carbon dioxide separation method using the composite separation membrane.
従来より、高分子素材には、その素材に特有の気体透過性があるため、高分子素材から構成された膜によって、気体成分を分離できることが知られている（例えば、非特許文献１参照）。特に、膜による気体成分の分離技術は、エネルギーが少ない、装置が小型化できる、装置のメンテナンスが容易になる等の利点があり、種々の分野で使用されている。近年、膜により気体成分を分離する技術の中でも、二酸化炭素を選択的に分離する技術が精力的に検討されている。この技術は、油田のオフガス、ゴミ焼却や火力発電の排ガス、天然ガス等からの二酸化炭素の分離回収に利用することができる。 Conventionally, since a polymer material has gas permeability unique to the material, it is known that a gas component can be separated by a film composed of the polymer material (see, for example, Non-Patent Document 1). . In particular, a gas component separation technique using a membrane has advantages such as low energy consumption, miniaturization of the apparatus, and easy maintenance of the apparatus, and is used in various fields. In recent years, a technique for selectively separating carbon dioxide among techniques for separating a gas component by a membrane has been energetically studied. This technology can be used to separate and recover carbon dioxide from off-gas in oil fields, waste incineration, exhaust gas from thermal power generation, natural gas, and the like.
しかしながら、従来の複合膜では二酸化炭素の選択性（二酸化炭素の膜透過速度／分離対象ガスの膜透過速度）が不十分で、目的とする濃度で二酸化炭素を回収することが出来なかった。そのため、二酸化炭素選択性に優れた分離膜の開発が望まれていた。このような膜を得るために、二酸化炭素に対して選択的に親和性が高い素材を用いることが提案されている。例えば、室温で液状物質であるポリアミドアミンデンドリマーを、微多孔質の支持体に含浸させた分離膜が提案されている（非特許文献２および３）。この含浸膜の分離性能を、ヘリウムキャリアー法と言う膜に圧力差を設けない方法を用いて測定すると、二酸化炭素選択性が１０００を超える優れた二酸化炭素選択性を示した。しかしながら、液状物質であるポリアミドアミンデンドリマーを微多孔質の支持体に含浸させた分離膜では、この膜に圧力を掛けると、含浸させたデンドリマーが時間と共に支持体から抜け出して、性能を維持できないため、実用に供することが困難である。 However, the conventional composite membrane has insufficient carbon dioxide selectivity (the membrane permeation rate of carbon dioxide / the membrane permeation rate of the separation target gas), and carbon dioxide could not be recovered at the target concentration. Therefore, development of a separation membrane having excellent carbon dioxide selectivity has been desired. In order to obtain such a membrane, it has been proposed to use a material having a high selective affinity for carbon dioxide. For example, a separation membrane in which a polyamidoamine dendrimer that is a liquid substance at room temperature is impregnated in a microporous support has been proposed (Non-patent Documents 2 and 3). When the separation performance of this impregnated membrane was measured by using a method called a helium carrier method in which no pressure difference was provided to the membrane, the carbon dioxide selectivity was excellent and the carbon dioxide selectivity exceeding 1000 was shown. However, in a separation membrane in which a polyamidoamine dendrimer, which is a liquid material, is impregnated in a microporous support, if the pressure is applied to the membrane, the impregnated dendrimer escapes from the support over time, and the performance cannot be maintained. It is difficult to put to practical use.
そのため、ポリアミドアミンデンドリマーのような二酸化炭素に選択的に強い親和性を有する物質を固定して、実用的な圧力差をかけることが可能な複合膜の開発が切望されており、例えば、以下のような複合膜が提案されている。 Therefore, the development of a composite membrane capable of immobilizing a substance having a selective strong affinity for carbon dioxide such as a polyamidoamine dendrimer and applying a practical pressure difference has been desired. For example, Such composite membranes have been proposed.
特許文献１では、多孔質性の支持膜（Ａ）の表面に、アミノ基および／または水酸基を有する高分子材料（ａ）が多官能性の架橋剤（ｂ）で架橋されてなる吸水性高分子材料と、特定のアミドアミン基を有するアミン化合物（ｃ）とからなる気体分離層を形成した複合膜が提案されている。 In Patent Document 1, a high water-absorbing property is obtained in which a polymer material (a) having an amino group and / or a hydroxyl group is cross-linked with a polyfunctional cross-linking agent (b) on the surface of a porous support membrane (A). There has been proposed a composite membrane in which a gas separation layer comprising a molecular material and an amine compound (c) having a specific amidoamine group is formed.
また、特許文献２では、多官能重合性単量体を重合させて得られる高分子重合体内に、特定のアミドアミン基を有するアミン化合物が固定化されてなる高分子膜と多孔質支持膜とを積層させてなる複合膜が提案されている。 Further, in Patent Document 2, a polymer film obtained by immobilizing an amine compound having a specific amide amine group and a porous support film in a polymer obtained by polymerizing a polyfunctional polymerizable monomer. A laminated composite film has been proposed.
しかし、特許文献１及び２の複合膜に関しては、供給ガスに含まれる水分によって気体分離層又は高分子膜の表面に結露が生じた場合、その結露水中に水溶性のアミン化合物が溶出してしまい、複合膜の分離性能が次第に低下してくるという問題があった。 However, regarding the composite membranes of Patent Documents 1 and 2, when condensation occurs on the surface of the gas separation layer or the polymer membrane due to moisture contained in the supply gas, a water-soluble amine compound is eluted in the condensed water. There is a problem that the separation performance of the composite membrane gradually decreases.
一方、特許文献３では、無機多孔質支持体中に５％熱重量減少温度が２５０℃以上であるイオン液体またはイオン液体を重合させたポリマーゲルを含んだ液膜と、イオン液体を透過させない５％熱重量減少温度が２５０℃以上の膜である封止膜とを有し、二層の封止膜によって液膜が挟まれた多層構造を有する二酸化炭素濃縮膜が提案されている。 On the other hand, in Patent Document 3, a liquid film containing an ionic liquid or a polymer gel obtained by polymerizing an ionic liquid having a 5% thermal weight loss temperature of 250 ° C. or higher in an inorganic porous support and an ionic liquid not permeated 5. A carbon dioxide-enriched membrane having a multilayer structure in which a liquid film is sandwiched between two layers of sealing films is proposed.
そして、特許文献３には、液膜を挟んで二層の封止膜が存在することにより、イオン液体（もしくはイオン液体を重合させたポリマーゲル）の消失を防ぐことができることが記載されている。また、封止膜の材料として、ポリイミド、ポリジフェニルアセチレン、ポリトリメチルシリルプロピン等の有機材料；ＭＦＩ型、ＣＨＡ型（特にＳＡＰＯ３４）、ＤＤＲ型、Ｔ型等のゼオライト；ポリジメチルシロキサン等のゴム；もしくはこれらの複合材料が記載されている。 Patent Document 3 describes that the disappearance of the ionic liquid (or polymer gel obtained by polymerizing the ionic liquid) can be prevented by the presence of the two-layer sealing film with the liquid film interposed therebetween. . Moreover, as a material of the sealing film, organic materials such as polyimide, polydiphenylacetylene, polytrimethylsilylpropyne; zeolites such as MFI type, CHA type (especially SAPO34), DDR type, T type; rubber such as polydimethylsiloxane; Alternatively, these composite materials are described.
本発明は、結露耐性が高く、高分子膜中のアミン化合物が溶出しにくい複合分離膜を提供することを目的とする。 An object of the present invention is to provide a composite separation membrane that has high resistance to dew condensation and is difficult to elute an amine compound in a polymer membrane.
本発明者らは、前記課題を解決すべく鋭意検討したところ、以下に示す複合分離膜により上記目的を達成できることを見出し、本発明を完成するに至った。 The present inventors diligently studied to solve the above-mentioned problems. As a result, they found that the above object can be achieved by the composite separation membrane shown below, and have completed the present invention.
即ち、本発明は、高分子重合体及びアミン化合物を含む高分子膜と、多孔質支持膜とが積層されている複合分離膜において、
前記アミン化合物は、下記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を有しており、かつ前記高分子膜の両面に疎水性層が積層されていることを特徴とする複合分離膜、に関する。
（式中、Ａ１は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。）
（式中、Ａ２は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。）
That is, the present invention relates to a composite separation membrane in which a polymer membrane containing a polymer and an amine compound and a porous support membrane are laminated.
The amine compound has an amidoamino group represented by the following formula [I] and / or [II], and a hydrophobic layer is laminated on both surfaces of the polymer membrane. Membrane.
(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
前記疎水性層は、純水に対する接触角が１０°以上であることが好ましい。 The hydrophobic layer preferably has a contact angle with respect to pure water of 10 ° or more.
また、疎水性層の形成材料は、シリコーンエラストマーであることが好ましい。 The material for forming the hydrophobic layer is preferably a silicone elastomer.
さらに、本発明の二酸化炭素の分離方法は、二酸化炭素を含む混合ガスを、前記複合分離膜に接触させて、該混合ガス中の二酸化炭素を選択的に透過させる工程を含むことを特徴とする。 Furthermore, the carbon dioxide separation method of the present invention includes a step of bringing a mixed gas containing carbon dioxide into contact with the composite separation membrane to selectively permeate carbon dioxide in the mixed gas. .
本発明の複合分離膜は、実用に供する圧力差において、高い選択性をもって二酸化炭素を他のガスから分離することができる。また、高分子膜の両面に疎水性層が積層されているため、たとえ供給ガス中の水分によって結露が発生したとしても、疎水性層によって高分子膜が結露水と接触することを防止することができ、高分子膜中のアミン化合物の溶出を効果的に防止することができる。そのため、従来の複合膜のように、アミン化合物の溶出によって分離性能が次第に低下することがない。なお、本発明の複合分離膜は、二酸化炭素分離能を有するアミン化合物が高分子膜の表面に担持されているのではなく、高分子膜内に固定化されており、かつ高分子膜が多孔質支持膜上に積層されているため、分離性能の安定性が非常に優れている。 The composite separation membrane of the present invention can separate carbon dioxide from other gases with high selectivity at practical pressure differences. In addition, since the hydrophobic layers are laminated on both sides of the polymer membrane, even if condensation occurs due to moisture in the supply gas, the hydrophobic membrane prevents the polymer membrane from coming into contact with the condensed water. And the elution of the amine compound in the polymer film can be effectively prevented. Therefore, unlike the conventional composite membrane, the separation performance does not gradually deteriorate due to elution of the amine compound. In the composite separation membrane of the present invention, the amine compound having carbon dioxide separation ability is not supported on the surface of the polymer membrane, but is immobilized in the polymer membrane, and the polymer membrane is porous. Since it is laminated on the quality support membrane, the stability of the separation performance is very excellent.
本発明の複合分離膜は、高分子重合体及びアミン化合物を含む高分子膜と、多孔質支持膜とが積層されているものであり、
前記アミン化合物は、下記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を有しており、かつ前記高分子膜の両面に疎水性層が積層されていることを特徴とする。
（式中、Ａ１は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。）
（式中、Ａ２は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。）
なお、本発明において複合分離膜とは、ガス分離能を有する高分子膜、疎水性層、及び多孔質支持膜が一体に形成されたものをいう。
The composite separation membrane of the present invention is a laminate of a polymer membrane containing a polymer and an amine compound and a porous support membrane,
The amine compound has an amidoamino group represented by the following formula [I] and / or [II], and a hydrophobic layer is laminated on both surfaces of the polymer film.
(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
In the present invention, the composite separation membrane refers to one in which a polymer membrane having gas separation ability, a hydrophobic layer, and a porous support membrane are integrally formed.
高分子重合体内に固定化されるアミン化合物は、前記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を有するアミン化合物である。式［Ｉ］又は［ＩＩ］中、Ａ１又はＡ２で示される炭素数１〜３の二価有機残基としては、例えば、直鎖状又は分枝状の炭素数１〜３のアルキレン基が挙げられる。このようなアルキレン基の具体例としては、−ＣＨ２−、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ（ＣＨ３）−等が挙げられ、これらのうち特に−ＣＨ２−が好ましい。 The amine compound immobilized in the polymer is an amine compound having an amide amino group represented by the formula [I] and / or [II]. In the formula [I] or [II], the divalent organic residue having 1 to 3 carbon atoms represented by A 1 or A 2 is, for example, a linear or branched alkylene group having 1 to 3 carbon atoms. Is mentioned. Specific examples of such alkylene groups, -CH 2 -, - CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) - , and the like, Of these, —CH 2 — is particularly preferable.
アミン化合物は、式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を１個以上有していればよく、アミドアミノ基の数は特に制限されないが、２〜４０９６個有していることが好ましく、より好ましくは３〜１２８個である。 The amine compound only needs to have one or more amidoamino groups represented by the formula [I] and / or [II], and the number of amidoamino groups is not particularly limited, but it should be 2 to 4096. The number is preferably 3 to 128.
また、アミン化合物において、アミドアミノ基が占める重量分率は特に制限されない。二酸化炭素と水素の分離能を高める観点から、アミドアミノ基が占める重量分率は５％以上であることが好ましく、より好ましくは１０〜９４％であり、さらに好ましくは１５〜５３％である。 In the amine compound, the weight fraction occupied by the amide amino group is not particularly limited. From the viewpoint of enhancing the separation ability of carbon dioxide and hydrogen, the weight fraction occupied by the amide amino group is preferably 5% or more, more preferably 10 to 94%, and further preferably 15 to 53%.
前記アミン化合物において、式［Ｉ］又は［ＩＩ］で示されるアミドアミノ基が結合する骨格としては、例えば次のものが挙げられる。
すなわち、本発明で用いるアミン化合物は、式［Ｉ］又は［ＩＩ］で示されるアミドアミノ基が、上記式において米印の結合子の一部または全部に、直接またはアルキレン基を介して結合し、アミドアミノ基が結合してない結合子には、水素原子、アルキル基、アミノアルキル基、ヒドロキシアルキル基等が結合した化合物である。 That is, in the amine compound used in the present invention, the amidoamino group represented by the formula [I] or [II] is bonded directly or via an alkylene group to a part or all of the asterisks in the above formula, A compound in which a hydrogen atom, an alkyl group, an aminoalkyl group, a hydroxyalkyl group, or the like is bonded to a connector to which an amidoamino group is not bonded.
前記アミン化合物としては、例えば、下記式で示される第０世代のポリアミドアミン系デンドリマー、及びこれら第０世代ポリアミドアミン系デンドリマーに対応する第１世代以上のものが挙げられる。
上記ポリアミドアミン系デンドリマーのうち、特に好適な化合物の一例として、下記ポリアミドアミン系デンドリマーが挙げられる。
なお、本発明で用いるポリアミドアミン系デンドリマーは、枝の長さがすべて等しいものと、そのうちの少なくとも１つがヒドロキシアルキル基またはアルキル基で置換され、枝の長さが異なるものを含む。また、表面基（すなわち、式［Ｉ］又は［ＩＩ］で示されるアミドアミン基）の数が異なる各種のポリアミドアミン系デンドリマーを使用することができる。ポリアミドアミン系デンドリマーの表面基の数と世代の関係は、第０世代の表面基の数をａ（ａは３以上の整数を示す。）とすると、第ｂ世代（ｂは整数を示す。）の表面基の数ｃは、次の通りである。
式［Ｉ］で示されるアミドアミン基を有するアミン化合物は、公知の有機合成法に従って製造することができる。当該アミン化合物の合成方法の一例として、メチルエステル基を有する母核化合物と、下記式［Ｉａ］で示されるアミン化合物を反応させる方法が例示される。かかる方法によれば、メチルエステル基を有する化合物の該メチルエステル基が式［Ｉ］で示されるアミドアミン基に変換されて、式［ＩＩ］で示されるアミドアミン基を有するアミン化合物を製造することができる。下式は、当該合成法において、メチルエステル基が式［Ｉ］で示されるアミドアミン基に変換される式である。
メチルエステル基を有する化合物と、式［Ｉａ］で示されるアミン化合物との反応は、メチルエステル基を有する化合物１モルに対して、式［Ｉａ］で示されるアミン化合物を、通常約３〜２０モル、好ましくは約５〜１０モルの割合で行われる。メチルエステル基を有する化合物と、式［Ｉａ］で示されるアミン化合物との反応は、通常、適当な溶媒中で行われる。溶媒としては、反応を阻害しない溶媒であれば公知のものを広く使用できる。溶媒としては、例えば、メタノール、エタノール、２−プロパノール、テトラヒドロフラン、１，４−ジオキサン等が挙げられる。これらの溶媒には、水が含まれていてもよい。反応は、通常約０〜４０℃、好ましくは約２０〜３０℃で、約９０〜１８０時間、好ましくは約１６０〜１７０時間撹拌を続けることにより行われる。原料として用いられるメチルエステル基を有する化合物、及び式［Ｉａ］で示されるアミン化合物は公知の化合物を用いることができる。上記反応によって得られた反応混合物を、例えば、冷却した後、濾過、濃縮、抽出等の単離操作に供して粗反応生成物を分離し、更に必要に応じてカラムクロマトグラフィー、再結晶等の通常の精製操作を行うことによって式［Ｉ］で示されるアミドアミン基を有するアミン化合物を単離精製することができる。 The reaction between the compound having a methyl ester group and the amine compound represented by the formula [Ia] is usually carried out by converting the amine compound represented by the formula [Ia] to about 3 to 20 per 1 mol of the compound having a methyl ester group. Mol, preferably about 5 to 10 mol. The reaction between the compound having a methyl ester group and the amine compound represented by the formula [Ia] is usually carried out in a suitable solvent. As the solvent, known solvents can be widely used as long as they do not inhibit the reaction. Examples of the solvent include methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane and the like. These solvents may contain water. The reaction is usually carried out at about 0 to 40 ° C., preferably about 20 to 30 ° C., by continuing stirring for about 90 to 180 hours, preferably about 160 to 170 hours. Known compounds can be used as the compound having a methyl ester group used as a raw material and the amine compound represented by the formula [Ia]. The reaction mixture obtained by the above reaction is cooled, for example, and then subjected to an isolation operation such as filtration, concentration, extraction, etc. to separate the crude reaction product, and further, if necessary, column chromatography, recrystallization, etc. The amine compound having an amidoamine group represented by the formula [I] can be isolated and purified by performing a normal purification operation.
また、式［ＩＩ］で示されるアミドアミン基を有するアミン化合物は、アミノ基を有する母核化合物と下記式［ＩＩａ］で示される末端にメチルエステル基を有するアミン化合物を、前記と同様に反応させることにより製造することができる。
高分子膜の形成材料である高分子重合体は特に制限されないが、架橋されたポリビニルアルコール、又は多官能重合性単量体を重合させて得られる高分子重合体を用いることが好ましい。 The polymer that is a material for forming the polymer film is not particularly limited, but it is preferable to use a polymer obtained by polymerizing a cross-linked polyvinyl alcohol or a polyfunctional polymerizable monomer.
ポリビニルアルコールを架橋させる架橋剤は特に制限されないが、下記式（１）にて表される架橋剤を用いることが好ましい。
Ｍ（ＯＲ１）ｎ （１）
（式中、Ｍは三価以上の金属原子を示し、ｎは３〜６の整数を示し、Ｒ１は、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数３〜１０のシクロアルキル基、炭素数３〜１０のシクロアルケニル基、炭素数６〜１０のアリール基、炭素数７〜１２のアラルキル基、炭素数２〜７のアシル基、式−ＮＨＲ２で示される基（式中、Ｒ２は、炭素数１〜６のアルキル基を示す。）、式−ＮＲ３Ｒ４で示される基（式中、Ｒ３及びＲ４は、それぞれ独立に、炭素数１〜６のアルキル基を示す。）、式−Ｃ（Ｏ）−ＮＨＲ５で示される基（式中、Ｒ５は、炭素数１〜６のアルキル基を示す。）、式−Ｃ（Ｏ）−ＮＲ６Ｒ７で示される基（式中、Ｒ６及びＲ７は、それぞれ独立に、炭素数１〜６のアルキル基を示す。）、又は１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環基を示し、これらは互いに結合して環構造を形成していてもよく、これらの基又は環は置換基を有していてもよい。）
The crosslinking agent for crosslinking polyvinyl alcohol is not particularly limited, but a crosslinking agent represented by the following formula (1) is preferably used.
M (OR 1 ) n (1)
(In the formula, M represents a trivalent or higher metal atom, n represents an integer of 3 to 6, R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 3 carbon atoms. 10 cycloalkyl group, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group having 2 to 7 carbon atoms, represented by the formula -NHR 2 Group (wherein R 2 represents an alkyl group having 1 to 6 carbon atoms) and a group represented by the formula —NR 3 R 4 (wherein R 3 and R 4 are each independently a carbon number) 1 to 6 alkyl group), a group represented by formula -C (O) -NHR 5 (wherein R 5 represents an alkyl group having 1 to 6 carbon atoms), formula -C (O ) -NR 6 group (wherein represented by R 7, R 6 and R 7 each independently represent an alkyl group having 1 to 6 carbon atoms.), or Represents a 5- to 10-membered heterocyclic group containing 3 oxygen atoms, nitrogen atoms or sulfur atoms, which may be bonded to each other to form a ring structure, and these groups or rings have a substituent. You may do it.)
前記式（１）で示される架橋剤について詳細に説明する。式（１）におけるＭは三価以上の金属原子を示す。三価以上の金属原子としては、チタン、ジルコニウム、アルミニウム又はコバルト等が挙げられ、好ましくはチタンである。Ｒ１の炭素数１〜６のアルキル基は、直鎖もしくは分枝状であってよく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ペンチル基、イソヘキシル基、又はヘキシル基が挙げられる。Ｒ１の炭素数２〜６のアルケニル基は、直鎖もしくは分枝状であってよく、具体的には、アリル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、３−ブテニル基、２−ブテニル基、１−ブテニル基、１−メチル−２−プロペニル基、１−メチル−１−プロペニル基、１−エチル−１−エテニル基、２−メチル−２−プロペニル基、２−メチル−１−プロペニル基、３−メチル−２−ブテニル基、４−ペンテニル基が挙げられる。Ｒ１の炭素数３〜１０のシクロアルキル基は、具体的には、シクロプロピル基、２−メチルシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、 シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基等が挙げられる。Ｒ１の炭素数３〜１０のシクロアルケニル基は、具体的には、１−シクロプロペニル基、２−シクロプロペニル基、１−シクロブテニル基、２−シクロブテニル基、１−シクロペンテニル基、２−シクロペンテニル基、３−シクロペンテニル基、１−シクロヘキセニル基、２−シクロヘキセニル基、３−シクロヘキセニル基、１−シクロヘプテニル基、２−シクロヘプテニル基、３−シクロヘプテニル基、４−シクロヘプテニル基、１−シクロオクテニル基、２−シクロオクテニル基、３−シクロオクテニル基、４−シクロオクテニル基、１−シクロノネニル基、２−シクロノネニル基、３−シクロノネニル基、４−シクロノネニル基、１−シクロデセニル基、２−シクロデセニル基、３−シクロデセニル基、４−シクロデセニル基、２，４−シクロペンタジエニル基、２，５−シクロヘキサジエニル基、２，４−シクロヘプタジエニル基、２，６−シクロヘブタジエニル基等が挙げられる。Ｒ１の炭素数６〜１０のアリール基は、具体的にはフェニル基、ナフチル基が挙げられる。Ｒ１の炭素数７〜１２のアラルキル基は、具体的には、ベンジル基、フェネチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルヘキシル基、ナフチルメチル基、ナフチルエチル基、ジフェニルメチル基等が挙げられる。Ｒ１の炭素数２〜７のアシル基は、具体的には、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピバロイル基、ベンゾイル基が挙げられる。Ｒ１の式−ＮＨＲ２で示される基（式中、Ｒ２は、炭素数１〜６のアルキル基を示す。）、式−ＮＲ３Ｒ４で示される基（式中、Ｒ３及びＲ４は、それぞれ独立に、炭素数１〜６のアルキル基を示す。）、式−Ｃ（Ｏ）−ＮＨＲ５で示される基（式中、Ｒ５は、炭素数１〜６のアルキル基を示す。）、式−Ｃ（Ｏ）−ＮＲ６Ｒ７で示される基（式中、Ｒ６及びＲ７は、それぞれ独立に、炭素数１〜６のアルキル基を示す。）におけるＲ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６及びＲ７の炭素数１〜６のアルキル基は、前記したものと同様である。Ｒ１の１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環基は、５〜１０員脂肪族複素環基であってもよいし、５〜１０員芳香族複素環基であってもよい。１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む、５〜１０員複素環基としては、フラン、チオフェン、ピロール、２Ｈ−ピロール、ピラン、チオピラン、ピリジン、オキサゾール、イソキサゾール、チアゾール、イソチアゾール、フラザン、イミダゾール、ピラゾール、ピロリジン、イミダゾリジン、ピラゾリジン、ピペリジン、ピペラジン、ピロリン、イミダゾリン、ピラゾリン、モルフォリン、アゼピン、アゾシン等が挙げられる。「１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環基」は、飽和環基であってもよいし、不飽和環基であってもよい。「１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環」は、「１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜８員複素環」が好ましく、「１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜７員複素環」が更に好ましい。また、「１〜３個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環」は、「１〜２個の酸素原子、窒素原子若しくは硫黄原子を含む５〜１０員複素環」が好ましく、「１〜２個の酸素原子、窒素原子若しくは硫黄原子を含む５〜８員複素環」が更に好ましく、「１〜２個の酸素原子、窒素原子若しくは硫黄原子を含む５〜７員複素環」が更になお好ましい。 The crosslinking agent represented by the formula (1) will be described in detail. M in the formula (1) represents a trivalent or higher metal atom. Examples of the trivalent or higher metal atom include titanium, zirconium, aluminum, and cobalt, and titanium is preferable. The alkyl group having 1 to 6 carbon atoms of R 1 may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert group. -A butyl group, a butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a pentyl group, an isohexyl group, or a hexyl group. The alkenyl group having 2 to 6 carbon atoms of R 1 may be linear or branched, and specifically includes an allyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, and 3-butenyl group. 2-butenyl group, 1-butenyl group, 1-methyl-2-propenyl group, 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl A -1-propenyl group, a 3-methyl-2-butenyl group, and a 4-pentenyl group are exemplified. Specific examples of the cycloalkyl group having 3 to 10 carbon atoms of R 1 include a cyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, A cyclodecyl group etc. are mentioned. Specific examples of the cycloalkenyl group having 3 to 10 carbon atoms of R 1 include 1-cyclopropenyl group, 2-cyclopropenyl group, 1-cyclobutenyl group, 2-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclo Pentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group, 4-cycloheptenyl group, 1-cyclooctenyl group Group, 2-cyclooctenyl group, 3-cyclooctenyl group, 4-cyclooctenyl group, 1-cyclononenyl group, 2-cyclononenyl group, 3-cyclononenyl group, 4-cyclononenyl group, 1-cyclodecenyl group, 2-cyclodecenyl group, 3-cyclodecenyl group Group, 4-cyclodecenyl group, 2,4 -Cyclopentadienyl group, 2,5-cyclohexadienyl group, 2,4-cycloheptadienyl group, 2,6-cyclohebutadienyl group and the like can be mentioned. Specific examples of the aryl group having 6 to 10 carbon atoms of R 1 include a phenyl group and a naphthyl group. Specific examples of the aralkyl group having 7 to 12 carbon atoms of R 1 include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, naphthylmethyl group, naphthylethyl group, diphenylmethyl. Groups and the like. Specific examples of the acyl group having 2 to 7 carbon atoms of R 1 include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, and benzoyl group. A group represented by the formula —NHR 2 of R 1 (wherein R 2 represents an alkyl group having 1 to 6 carbon atoms), a group represented by the formula —NR 3 R 4 (wherein R 3 and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms, and a group represented by the formula —C (O) —NHR 5 (wherein R 5 represents an alkyl group having 1 to 6 carbon atoms). shown.), the radical (wherein the formula -C (O) -NR 6 R 7 , R 6 and R 7 are each independently, R 2 in the shown.) the alkyl group having 1 to 6 carbon atoms, The alkyl group having 1 to 6 carbon atoms of R 3 , R 4 , R 5 , R 6 and R 7 is the same as described above. The 5- to 10-membered heterocyclic group containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms of R 1 may be a 5- to 10-membered aliphatic heterocyclic group, or a 5- to 10-membered aromatic heterocycle. It may be a cyclic group. Examples of the 5- to 10-membered heterocyclic group containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms include furan, thiophene, pyrrole, 2H-pyrrole, pyran, thiopyran, pyridine, oxazole, isoxazole, thiazole and isothiazole. , Furazane, imidazole, pyrazole, pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine, pyrroline, imidazoline, pyrazoline, morpholine, azepine, azocine and the like. The “5- to 10-membered heterocyclic group containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms” may be a saturated ring group or an unsaturated ring group. The “5- to 10-membered heterocyclic ring containing 1 to 3 oxygen atoms, nitrogen atom or sulfur atom” is preferably “5- to 8-membered heterocyclic ring containing 1 to 3 oxygen atoms, nitrogen atom or sulfur atom”. "5- to 7-membered heterocycle containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms" is more preferable. Further, “a 5- to 10-membered heterocyclic ring containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms” means “a 5- to 10-membered heterocyclic ring containing 1 to 2 oxygen atoms, nitrogen atoms or sulfur atoms”. Is more preferable, and “5- to 8-membered heterocycle containing 1 to 2 oxygen atoms, nitrogen atoms or sulfur atoms” is more preferable, and “5 to 7-membered containing 1 to 2 oxygen atoms, nitrogen atoms or sulfur atoms”. “Heterocycle” is still more preferred.
前記したＲ１のＭ及び基は互いに結合して環構造を形成していてもよい。前記したＲ１の基又は環は置換基を有していてもよい。これらの基又は環が有していてもよい置換基としては、例えばフッ素原子、塩素原子、臭素原子又はヨウ素原子のハロゲン原子；クロロメチル基、２−クロロエチル基、３−クロロエチル基、又はトリフルオロメチル基等の炭素数１〜６のハロゲン化アルキル基；メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ペンチル基、イソヘキシル基、又はヘキシル基等の炭素数１〜６のアルキル基；メトキシ基、エトキシ基、ｎ−プロピルオキシ基、ｎ−ブトキシ基、又はｎ−ヘキシルオキシ基等の炭素数１〜６のアルコキシ基；シアノ基；フェノキシ基；アミノ基；水酸基；等が好ましい例として挙げられる。 The M and group of R 1 described above may be bonded to each other to form a ring structure. The group or ring of R 1 described above may have a substituent. Examples of the substituent that these groups or rings may have include a halogen atom of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a chloromethyl group, a 2-chloroethyl group, a 3-chloroethyl group, or trifluoro A halogenated alkyl group having 1 to 6 carbon atoms such as a methyl group; methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, butyl group, isopentyl group, neopentyl group, tert -C1-C6 alkyl group such as pentyl group, pentyl group, isohexyl group, or hexyl group; carbon such as methoxy group, ethoxy group, n-propyloxy group, n-butoxy group, or n-hexyloxy group Preferred examples include an alkoxy group having 1 to 6; a cyano group; a phenoxy group; an amino group; a hydroxyl group;
上記架橋剤のうち、下記式にて表される架橋剤を用いることが好ましい。
Ｔｉ（ＯＲ１）４
（式中、Ｒ１は、前記と同様である。）
Among the crosslinking agents, it is preferable to use a crosslinking agent represented by the following formula.
Ti (OR 1 ) 4
(Wherein R 1 is the same as described above.)
特に、下記式にて表される架橋剤を用いることが好ましい。
（式中、ｔ−Ｂｕはｔｅｒｔ−ブチル基を示す。）
(In the formula, t-Bu represents a tert-butyl group.)
チタン系架橋剤は、ＰＶＡの水酸基と架橋反応する一方で、デンドリマーのアミノ基との反応性が低く、デンドリマーとは反応し難いため架橋剤として特に好ましい。 The titanium-based crosslinking agent is particularly preferable as a crosslinking agent because it has a crosslinking reaction with the hydroxyl group of PVA, but has low reactivity with the amino group of the dendrimer and hardly reacts with the dendrimer.
ポリビニルアルコールは水溶液の形態で用いることが好ましい。この場合、水溶液の濃度は０.５〜３０重量％、好ましくは１〜１０重量％である。ポリビニルアルコールの重量平均分子量は、通常約５千〜１００万、好ましくは約４万〜４０万である。重合度でいえば、通常約１１０〜２３０００、好ましくは約１，０００〜１０，０００である。ＰＶＡが水酸基を有する親水性のポリマーであることから、デンドリマーとの相溶性に優れる上、ＰＶＡのガス透過量が小さく、ＰＶＡ部分を通過するガス量が少ないため、他のポリマーに比べて、ガス分離膜の材料としてＰＶＡは優れている。 Polyvinyl alcohol is preferably used in the form of an aqueous solution. In this case, the concentration of the aqueous solution is 0.5 to 30% by weight, preferably 1 to 10% by weight. The weight average molecular weight of polyvinyl alcohol is usually about 5,000 to 1,000,000, preferably about 40,000 to 400,000. In terms of the degree of polymerization, it is usually about 110 to 23,000, preferably about 1,000 to 10,000. Since PVA is a hydrophilic polymer having a hydroxyl group, it has excellent compatibility with dendrimers, and the gas permeation amount of PVA is small and the amount of gas passing through the PVA portion is small. PVA is excellent as a material for the separation membrane.
前記ポリビニルアルコール内に固定化される前記アミン化合物の量は、ポリビニルアルコール水溶液１００重量部に対して通常約１〜５０重量部、好ましくは約３〜２０重量部である。 The amount of the amine compound immobilized in the polyvinyl alcohol is usually about 1 to 50 parts by weight, preferably about 3 to 20 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol aqueous solution.
本発明の高分子膜としては、前記チタン系架橋剤で架橋されてなる、架橋部分と結晶部分を有するＰＶＡ内に、ポリアミドアミン系デンドリマーが固定されている高分子膜が特に好ましい。チタン系架橋剤は、ポリアミドアミン系デンドリマーとは反応せずに、ＰＶＡのみと反応する架橋剤であるため好ましく用いられる。 The polymer film of the present invention is particularly preferably a polymer film in which a polyamidoamine dendrimer is fixed in a PVA having a crosslinked part and a crystal part, which is crosslinked with the titanium-based crosslinking agent. The titanium-based crosslinking agent is preferably used because it is a crosslinking agent that reacts only with PVA without reacting with the polyamidoamine-based dendrimer.
一方、多官能重合性単量体は、炭素−炭素不飽和結合を２個以上有する重合可能な化合物であれば特に限定されない。例えば、多官能（メタ）アクリルアミド類、多官能（メタ）アクリレート類等の多官能アクリル系単量体；多官能ビニルエーテル類、ジビニルベンゼン等の多官能ビニル系単量体等が挙げられる。これらの多官能重合性単量体は、単独または２種類以上を組み合わせて用いることができる。 On the other hand, the polyfunctional polymerizable monomer is not particularly limited as long as it is a polymerizable compound having two or more carbon-carbon unsaturated bonds. Examples include polyfunctional acrylic monomers such as polyfunctional (meth) acrylamides and polyfunctional (meth) acrylates; polyfunctional vinyl monomers such as polyfunctional vinyl ethers and divinylbenzene. These polyfunctional polymerizable monomers can be used alone or in combination of two or more.
多官能（メタ）アクリルアミド類としては、Ｎ，Ｎ’−（１，２−ジヒドロキシエチレン）ビスアクリルアミド、エチジウムブロマイド−Ｎ，Ｎ’−ビスアクリルアミド（Ethidium bromide−Ｎ，Ｎ’−bisacrylamide）、エチジウムブロマイド−Ｎ，Ｎ’−ビスメタクリルアミド（Ethidium bromide−Ｎ，Ｎ’−bismethacrylamide）、Ｎ，Ｎ’−エチレンビスアクリルアミド、Ｎ，Ｎ’−メチレンビスアクリルアミド等が挙げられる。 Polyfunctional (meth) acrylamides include N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethidium bromide-N, N′-bisacrylamide, ethidium bromide -N, N'-bismethacrylamide (Ethidium bromide-N, N'-bismethacrylamide), N, N'-ethylenebisacrylamide, N, N'-methylenebisacrylamide and the like.
多官能（メタ）アクリレート類としては、ジ（メタ）アクリレート類、トリ（メタ）アクリレート類、テトラ（メタ）アクリレート類等が挙げられる。 Examples of polyfunctional (meth) acrylates include di (meth) acrylates, tri (meth) acrylates, and tetra (meth) acrylates.
ジ（メタ）アクリレート類としては、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオ−ルジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート等のアルキレングリコールジ（メタ）アクリレート類が挙げられる。 Di (meth) acrylates include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and trimethylolpropane di (meth). Examples include alkylene glycol di (meth) acrylates such as acrylate and pentaerythritol di (meth) acrylate.
トリ（メタ）アクリレート類としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリストールトリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等が挙げられる。 Examples of tri (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and glycerin tri (meth) acrylate.
テトラ（メタ）アクリレート類としては、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等が挙げられる。 Examples of tetra (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate.
多官能ビニルエーテル類としては、トリメチロールプロパントリビニルエーテル、ジトリメチロールプロパンテトラビニルエーテル、グリセリントリビニルエーテル等が挙げられる。 Examples of the polyfunctional vinyl ethers include trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, and the like.
また、必要に応じて、重合反応を上記多官能重合性単量体と単官能重合性単量体とを併用して行ってもよい。併用することにより、高分子重合体内の網目の大きさを調節することができる。 Moreover, you may perform a polymerization reaction using the said polyfunctional polymerizable monomer and a monofunctional polymerizable monomer together as needed. By using in combination, the size of the network in the polymer can be adjusted.
単官能重合性単量体としては、単官能（メタ）アクリルアミド類、単官能（メタ）アクリレート類等の単官能アクリル系単量体、単官能ビニルエーテル類、単官能Ｎ−ビニル化合物類または単官能ビニル化合物類等の単官能ビニル系単量体、単官能α，β−不飽和化合物類等が挙げられる。 Monofunctional polymerizable monomers include monofunctional acrylic monomers such as monofunctional (meth) acrylamides and monofunctional (meth) acrylates, monofunctional vinyl ethers, monofunctional N-vinyl compounds, or monofunctional And monofunctional vinyl monomers such as vinyl compounds, monofunctional α, β-unsaturated compounds, and the like.
単官能（メタ）アクリルアミド類としては、２−アセトアミドアクリル酸、（メタ）アクリルアミド、２−アクリルアミド−２−メチルプロパンスルホン酸、Ｎ−（ブトキシメチル）アクリルアミド、Ｎ−ｔｅｒｔ−ブチルアクリルアミド、ジアセトンアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−［３−（ジメチルアミノ）プロピル］メタクリルアミド等が挙げられる。 Monofunctional (meth) acrylamides include 2-acetamidoacrylic acid, (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N- (butoxymethyl) acrylamide, N-tert-butylacrylamide, diacetone acrylamide N, N-dimethylacrylamide, N- [3- (dimethylamino) propyl] methacrylamide and the like.
単官能（メタ）アクリレート類としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、（メタ）アクリル酸、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、（ポリ）エチレングリコールメタクリレート、ポリプロピレングリコール（メタ）アクリレート等が挙げられる。 Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxy Examples include polyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, (poly) ethylene glycol methacrylate, and polypropylene glycol (meth) acrylate.
単官能ビニルエーテル類としては、メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル、メトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル等が挙げられる。 Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, and the like.
単官能Ｎ−ビニル化合物類としては、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド等が挙げられる。 Examples of monofunctional N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.
単官能ビニル化合物類としては、スチレン、α−メチルスチレン、酢酸ビニル等が挙げられる。 Examples of monofunctional vinyl compounds include styrene, α-methylstyrene, vinyl acetate and the like.
単官能α，β−不飽和化合物類としては、無水マレイン酸、マレイン酸、マレイン酸ジメチル、マレイン酸ジエチル、フマル酸、フマル酸ジメチル、フマル酸ジエチル、フマル酸モノメチル、フマル酸モノエチル、無水イタコン酸、イタコン酸、イタコン酸ジメチル、メチレンマロン酸、メチレンマロン酸ジメチル、桂皮酸、桂皮酸メチル、クロトン酸、クロトン酸メチル等が挙げられる。 Monofunctional α, β-unsaturated compounds include maleic anhydride, maleic acid, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, itaconic anhydride , Itaconic acid, dimethyl itaconate, methylene malonic acid, dimethyl methylene malonate, cinnamic acid, methyl cinnamate, crotonic acid, methyl crotonic acid and the like.
高分子重合体内に固定化される式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を有するアミン化合物の量は、高分子重合体１００重量部に対して通常２〜４００重量部、好ましくは２５〜２５０重量部、さらに好ましくは４０〜１００重量部である。 The amount of the amine compound having an amide amino group represented by the formula [I] and / or [II] immobilized in the polymer is usually 2 to 400 parts by weight, preferably 100 parts by weight of the polymer. Is 25 to 250 parts by weight, more preferably 40 to 100 parts by weight.
本発明に用いる多孔質支持膜は、例えば、後述するポリマー等を用いて製造することができ、セラミックス又はポリエチレンテレフタレート（ＰＥＴ）フィルム等を用いることもできる。具体的には、ポリマーを用いて製造する場合、ポリマーを溶媒に溶解して、原料溶液を得たのち、該原料溶液と、凝固液（溶媒と非溶媒の混合溶液）と接触させて、非溶媒濃度の上昇により相分離を誘起する方法（非溶媒誘起相分離法；ＮＩＰＳ法、特公平１−２２００３号公報参照）により、多孔質支持膜を製造することができる。前記セラミックスとしては、アルミナ、ジルコニア、チタニア、シリカ等が挙げられる。 The porous support membrane used in the present invention can be produced using, for example, a polymer described later, and ceramics or polyethylene terephthalate (PET) film can also be used. Specifically, when producing using a polymer, the polymer is dissolved in a solvent to obtain a raw material solution, and then the raw material solution is brought into contact with a coagulation liquid (a mixed solution of a solvent and a non-solvent). A porous support membrane can be produced by a method of inducing phase separation by increasing the solvent concentration (non-solvent induced phase separation method; NIPS method, see Japanese Patent Publication No. 1-2003). Examples of the ceramic include alumina, zirconia, titania, and silica.
多孔質支持膜の製造に用いるポリマーとしては、例えば、ポリスルホン（ＰＳＦ）、ポリアリールエーテルスルホン、ポリフェニレンスルホン、トリアセチルセルロース、酢酸セルロース、ポリアクリロニトリル、ポリフッ化ビニリデン、芳香族ナイロン、ポリエチレンテレフタレ−ト（ＰＥＴ）、ポリエチレンナフタレート、ポリアリレート、ポリイミド、エポキシ樹脂、ポリエーテル、セロファン、芳香族ポリアミド、ポリエチレン、ポリプロピレン等が挙げられる。これらのうち、化学的、機械的に安定である観点から、ポリスルホン、ポリアリールエーテルスルホン、エポキシ樹脂を好ましく用いることができる。 Examples of the polymer used for the production of the porous support membrane include polysulfone (PSF), polyaryl ether sulfone, polyphenylene sulfone, triacetyl cellulose, cellulose acetate, polyacrylonitrile, polyvinylidene fluoride, aromatic nylon, polyethylene terephthalate. (PET), polyethylene naphthalate, polyarylate, polyimide, epoxy resin, polyether, cellophane, aromatic polyamide, polyethylene, polypropylene and the like. Of these, polysulfone, polyarylethersulfone, and epoxy resin can be preferably used from the viewpoint of being chemically and mechanically stable.
前記溶媒としては、Ｎ−メチルピロリドン（ＮＭＰ）、アセトン、ジメチルホルムアミド等が挙げられる。凝固時に凝固液へ溶媒が溶解するものであれば、特に限定されない。前記非溶媒としては、例えば水、一価アルコール、多価アルコール、エチレングリコール、テトラエチレングリコール等が挙げられる。 Examples of the solvent include N-methylpyrrolidone (NMP), acetone, dimethylformamide and the like. There is no particular limitation as long as the solvent dissolves in the coagulation liquid during coagulation. Examples of the non-solvent include water, monohydric alcohol, polyhydric alcohol, ethylene glycol, and tetraethylene glycol.
原料溶液の調製の際に、膨潤剤を添加して、凝固後の支持膜内の貫通孔を増加させ、ガス透過性を向上させることが好ましい。前記膨潤剤としては、例えばポリエチレングリコール、ポリビニルピロリドン、ヒドロキシプロピルセルロース、食塩、塩化リチウム、臭化マグネシウムから選ばれる１種または２種以上の混合物を用いることができる。この膨潤剤の中で、ポリエチレングリコールが好ましく、特に重量平均分子量４００〜８００のポリエチレングリコールが好ましい。原料溶液および凝固液の濃度は、原料溶液と凝固液とを接触させ、非溶媒誘起相分離法により多孔質支持膜を得られる濃度であれば特に限定されないが、例えば、原料のポリマーとしてポリアリールエーテルスルホンを用いる場合、原料溶液は、製膜性から２０〜３５ｗｔ％溶液とするのが好ましい。 In preparing the raw material solution, it is preferable to add a swelling agent to increase the number of through-holes in the support film after solidification and improve gas permeability. As the swelling agent, for example, one or a mixture of two or more selected from polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, sodium chloride, lithium chloride, and magnesium bromide can be used. Among these swelling agents, polyethylene glycol is preferable, and polyethylene glycol having a weight average molecular weight of 400 to 800 is particularly preferable. The concentration of the raw material solution and the coagulating liquid is not particularly limited as long as the porous solution is obtained by bringing the raw material solution and the coagulating liquid into contact with each other and a non-solvent induced phase separation method. When ether sulfone is used, the raw material solution is preferably a 20 to 35 wt% solution in view of film forming properties.
原料溶液と凝固液との接触の方法は特に限定されないが、例えば、原料溶液を凝固液に浸漬する方法が挙げられる。凝固液中の溶媒濃度は特に限定されないが、原料溶液の凝固において、凝固液中の溶媒濃度を変化させることにより支持膜の構造が変化し、耐圧性を上げることができる。 The method for contacting the raw material solution and the coagulating liquid is not particularly limited, and examples thereof include a method of immersing the raw material solution in the coagulating liquid. The concentration of the solvent in the coagulating liquid is not particularly limited, but in the coagulation of the raw material solution, changing the solvent concentration in the coagulating liquid changes the structure of the support film and can increase the pressure resistance.
多孔質支持膜の細孔の孔径としては、１００ｎｍ以下が好ましく、さらに好ましくは１０ｎｍ以下である。多孔質支持膜の膜厚は、高分子膜のガス透過性が多孔質支持膜のガス透過性よりも大きくならない範囲であれば特に限定されないが、通常２５〜１２５μｍであり、好ましくは４０〜７５μｍである。 The pore diameter of the pores of the porous support membrane is preferably 100 nm or less, more preferably 10 nm or less. The thickness of the porous support membrane is not particularly limited as long as the gas permeability of the polymer membrane does not become larger than the gas permeability of the porous support membrane, but is usually 25 to 125 μm, preferably 40 to 75 μm. It is.
機械的強度を付与するために、多孔質支持膜には織布又は不織布が積層されていてもよい。 In order to impart mechanical strength, a woven fabric or a nonwoven fabric may be laminated on the porous support membrane.
高分子膜の両面に積層される疎水性層は、水を透過しにくい疎水性ポリマーにより形成されていればよく、特に疎水性層の純水に対する接触角が１０°以上となるような疎水性ポリマーにより形成されていることが好ましい。接触角が１０°未満の場合には、結露水が疎水性層を浸透しやすくなり、高分子膜中のアミン化合物が溶出しやすくなる。 The hydrophobic layer laminated on both surfaces of the polymer film only needs to be formed of a hydrophobic polymer that does not easily transmit water. Particularly, the hydrophobic layer has a contact angle with respect to pure water of 10 ° or more. It is preferably formed of a polymer. When the contact angle is less than 10 °, the dew condensation water easily penetrates the hydrophobic layer, and the amine compound in the polymer film is easily eluted.
また、疎水性層は、ＣＯ２透過速度が１０−１１〜１０−７（ｍ３／ｍ２・Ｐａ・ｓ）であることが好ましい。ＣＯ２透過速度が低すぎると疎水性層がガス透過抵抗となり、複合分離膜のガス透過性能が低下する。一方、ＣＯ２透過速度が高すぎると疎水性層が多孔質になり、結露水が疎水性層を浸透しやすくなる。 The hydrophobic layer preferably has a CO 2 permeation rate of 10 −11 to 10 −7 (m 3 / m 2 · Pa · s). If the CO 2 permeation rate is too low, the hydrophobic layer becomes a gas permeation resistance, and the gas permeation performance of the composite separation membrane decreases. On the other hand, when the CO 2 permeation rate is too high, the hydrophobic layer becomes porous, and condensed water easily penetrates the hydrophobic layer.
疎水性層の形成材料である疎水性ポリマーとしては、例えば、シリコーンエラストマーなどのエラストマー、ポリテトラフルオロエチレンなどのフッ素樹脂、ポリ−１−トリメチルシリルプロピン、ポリジフェニルアセチレンなどが挙げられる。これらのうち、特にシリコーンエラストマーを用いることが好ましい。 Examples of the hydrophobic polymer that is a material for forming the hydrophobic layer include elastomers such as silicone elastomers, fluororesins such as polytetrafluoroethylene, poly-1-trimethylsilylpropyne, and polydiphenylacetylene. Of these, it is particularly preferable to use a silicone elastomer.
疎水性層の厚さは特に制限されないが、ガス透過性を高くし、かつ水透過性を低下させる観点から０．１〜１０μｍであることが好ましく、より好ましくは１〜５μｍである。 The thickness of the hydrophobic layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 1 to 5 μm from the viewpoint of increasing gas permeability and reducing water permeability.
以下に、本発明の複合分離膜の製造方法について説明する。 Below, the manufacturing method of the composite separation membrane of this invention is demonstrated.
本発明の複合分離膜の製造方法の第一態様としては、（１）基板上に疎水性ポリマーを含む有機溶液を塗布し、有機溶媒を除去して疎水性ポリマーを硬化させて疎水性層を形成する工程、（２）前記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミン基を有するアミン化合物の存在下で、少なくとも多官能重合性単量体を重合反応させることにより、又はポリビニルアルコールを架橋剤で架橋することにより、生成する高分子重合体内に前記アミン化合物を固定化させて高分子膜を形成する工程、及び（３）疎水性層、高分子膜、疎水性層、及び多孔質支持膜の順に各部材を積層する工程を含む方法が挙げられる。 As the first aspect of the method for producing a composite separation membrane of the present invention, (1) an organic solution containing a hydrophobic polymer is applied on a substrate, the organic solvent is removed and the hydrophobic polymer is cured to form a hydrophobic layer. (2) a polymerization reaction of at least a polyfunctional polymerizable monomer in the presence of an amine compound having an amidoamine group represented by the formula [I] and / or [II], or polyvinyl alcohol And (3) a hydrophobic layer, a polymer film, a hydrophobic layer, and a porous layer, and a step of immobilizing the amine compound in the resulting polymer polymer to form a polymer film. The method of including the process of laminating | stacking each member in order of a quality support film | membrane is mentioned.
（２）の製造工程において、前記アミン化合物の存在下で多官能重合性単量体を重合反応させる方法は、熱重合であっても光重合であってもよい。この場合、通常、熱重合開始剤又は光重合開始剤が用いられる。 In the production step (2), the method of polymerizing the polyfunctional polymerizable monomer in the presence of the amine compound may be thermal polymerization or photopolymerization. In this case, a thermal polymerization initiator or a photopolymerization initiator is usually used.
熱重合開始剤は公知のものを使用でき、例えば、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエー卜、ラウロイルパーオキサイド等の有機過酸化物；アゾビスイソブチロニトリル等のアゾ系化合物等が挙げられる。また、熱重合時には硬化促進剤を混合して使用してもよい。硬化促進剤としては、例えば、ナフテン酸コバルト、オクチル酸コバルト、３級アミン等が挙げられる。 Known thermal polymerization initiators can be used, such as methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, t-butyl. Organic peroxides such as peroxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile. Moreover, you may mix and use a hardening accelerator at the time of thermal polymerization. Examples of the curing accelerator include cobalt naphthenate, cobalt octylate, and tertiary amine.
熱重合開始剤の添加量は、多官能重合性単量体１００重量部に対して０．０１〜１０重量部であることが好ましく、より好ましくは０．１〜１重量部である。 It is preferable that the addition amount of a thermal-polymerization initiator is 0.01-10 weight part with respect to 100 weight part of polyfunctional polymerizable monomers, More preferably, it is 0.1-1 weight part.
光重合開始剤は公知のものを使用でき、例えば、以下のような化合物が挙げられる。これらは単独または２種以上の混合物として使用できる。 A well-known photoinitiator can be used, for example, the following compounds are mentioned. These can be used alone or as a mixture of two or more.
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン、そのアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、４−（１−ｔ−ブチルジオキシ−１−メチルエチル）アセトフェノン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類。 Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1 -T-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2) -Pro Le) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetophenone such as propanone oligomer.
２−メチルアントラキノン、２−アミルアントラキノン、２−ｔ−ブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジイソプロピルチオキサントン、２−クロロチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−（３−ジメチルアミノ−２−ヒドロキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロリド等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン、４−（１−ｔ−ブチルジオキシ−１−メチルエチル）ベンゾフェノン、３，３′，４，４′−テトラキス（ｔ−ブチルジオキシカルボニル）ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、３，３′，４，４′−テトラ（ｔ−ブチルパーオキシルカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−Ｎ，Ｎ−ジメチル−Ｎ−［２−（１−オキソ−２−プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４−ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；アシルフォスフィンオキサイド類；キサントン類。 Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone Thioxanthones such as -9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzofe 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) Benzophenones such as (oxy) ethyl] benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; acylphosphine oxides; xanthones.
光重合開始剤の添加量は、多官能重合性単量体１００重量部に対して０．５〜１０重量部であることが好ましく、より好ましくは２〜３重量部である。 The addition amount of the photopolymerization initiator is preferably 0.5 to 10 parts by weight, more preferably 2 to 3 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable monomer.
多官能重合性単量体を光硬化させる場合には、光重合開始剤と共に増感剤として塩基性化合物を用いることができる。塩基性化合物としてはアミンを用いることが好ましく、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノプロピルアミン、ジメチルプロピルアミン、モノエタノールアミン、ジエタノールアミン、エチレンジアミン、ジエチレントリアミン、ジメチルアミノエチルメタクリレート、ポリエチレンイミン等が挙げられる。これらの中で特に三級アミンが好適である。 When the polyfunctional polymerizable monomer is photocured, a basic compound can be used as a sensitizer together with the photopolymerization initiator. As the basic compound, an amine is preferably used. For example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl. Examples include methacrylate and polyethyleneimine. Of these, tertiary amines are particularly preferred.
三級アミンとしては、例えば、トリエタノールアミン、トリイソプロパノールアミン、トリブタノールアミン、メチルジエタノールアミン、メチルジイソプロパノールアミン、メチルジブタノールアミン、エチルジエタノールアミン、エチルジイソプロパノールアミン、エチルジブタノールアミン、プロピルジエタノールアミン、プロピルジイソプロパノールアミン、プロピルジブタノールアミン、ジメチルエタノールアミン、ジメチルイソプロパノールアミン、ジメチルブタノールアミン、ジエチルエタノールアミン、ジエチルイソプロパノールアミン、ジエチルブタノールアミン、ジプロピルエタノールアミン、ジプロピルイソプロパノールアミン、ジプロピルブタノールアミン、ジブチルエタノールアミン、ジブチルイソプロパノールアミン、ジブチルブタノールアミン、メチルエチルエタノールアミン、メチルエチルイソプロパノールアミン、メチルエチルブタノールアミン、ベンジルジエタノールアミン、Ｎ−フェニルジエタノールアミン、テトラエタノールエチレンジアミン、テトラプロパノールエチレンジアミン等が挙げられる。また、これら水酸基含有三級アミンにエチレンオキサイドを付加させてポリエチレングリコール鎖を導入したもの、水酸基含有三級アミンに水酸基と反応性を有する官能基を含有するモノマーを付加させて重合性二重結合を導入したもの、ポリマーまたはオリゴマーに三級アミノ基を導入したもの等を用いてもよい。これらのアミンは単独または２種以上を組み合わせて用いることができる。 Examples of the tertiary amine include triethanolamine, triisopropanolamine, tributanolamine, methyldiethanolamine, methyldiisopropanolamine, methyldibutanolamine, ethyldiethanolamine, ethyldiisopropanolamine, ethyldibutanolamine, propyldiethanolamine, propyl Diisopropanolamine, propyldibutanolamine, dimethylethanolamine, dimethylisopropanolamine, dimethylbutanolamine, diethylethanolamine, diethylisopropanolamine, diethylbutanolamine, dipropylethanolamine, dipropylisopropanolamine, dipropylbutanolamine, dibutylethanol Amine, dibutyl isopropanol Min, dibutyl butanolamine, methyl ethyl ethanolamine, methyl ethyl isopropanolamine, methyl ethyl butanol amine, benzyl diethanolamine, N- phenyl-diethanolamine, tetraethanol ethylenediamine, tetramethylenediamine propanol ethylenediamine, and the like. In addition, a polyethylene glycol chain is introduced by adding ethylene oxide to the hydroxyl group-containing tertiary amine, and a polymerizable double bond is added by adding a monomer containing a functional group reactive with a hydroxyl group to the hydroxyl group-containing tertiary amine. In addition, a polymer or oligomer having a tertiary amino group introduced may be used. These amines can be used alone or in combination of two or more.
増感剤の添加量は、光重合開始剤１００重量部に対して１〜１０重量部であることが好ましく、より好ましくは５〜８重量部である。 It is preferable that the addition amount of a sensitizer is 1-10 weight part with respect to 100 weight part of photoinitiators, More preferably, it is 5-8 weight part.
重合反応は、適当な溶媒中で、熱重合の場合は加熱により、光重合の場合は紫外線等の照射により行うことが好ましい。溶媒としては、前記アミン化合物及び多官能重合性単量体を溶解するものであれば特に限定されないが、通常アルコール（例えば、メタノール、エタノール等）が好適に使用できる。熱重合は、通常約４０〜９０℃、好ましくは約６０〜７０℃で、通常約２〜２４時間、好ましくは約５〜１０時間行われる。光重合は、通常約２００〜４００ｎｍ、好ましくは約２５０〜３６０ｎｍの紫外線を用いて、通常約３０秒〜１０分、好ましくは約１〜３分照射することにより行われる。なお、熱重合と光重合とは併用して行うこともでき、例えば、熱重合の後に光重合を行うか、光重合させた後に熱重合するか、あるいは光重合と熱重合を同時に行うこともできる。 The polymerization reaction is preferably carried out in an appropriate solvent by heating in the case of thermal polymerization and by irradiation with ultraviolet rays or the like in the case of photopolymerization. The solvent is not particularly limited as long as it dissolves the amine compound and the polyfunctional polymerizable monomer, but usually an alcohol (for example, methanol, ethanol, etc.) can be preferably used. The thermal polymerization is usually carried out at about 40 to 90 ° C., preferably about 60 to 70 ° C., usually for about 2 to 24 hours, preferably about 5 to 10 hours. The photopolymerization is usually performed by irradiation with ultraviolet rays of about 200 to 400 nm, preferably about 250 to 360 nm, usually for about 30 seconds to 10 minutes, preferably about 1 to 3 minutes. In addition, thermal polymerization and photopolymerization can be performed in combination. For example, photopolymerization can be performed after thermal polymerization, thermal polymerization can be performed after photopolymerization, or photopolymerization and thermal polymerization can be performed simultaneously. it can.
上記製造方法により、高分子重合体が生成すると同時に、該高分子重合体内に前記アミン化合物が固定化され、高分子膜が得られる。高分子膜としては、三次元網目構造を有する高分子重合体の該網目構造内に前記アミン化合物が封入され、固定化されているものが好適である。 By the above production method, a polymer is produced, and at the same time, the amine compound is immobilized in the polymer to obtain a polymer film. As the polymer film, a polymer film having a three-dimensional network structure in which the amine compound is sealed and immobilized is suitable.
（３）の製造工程において、疎水性層、高分子膜、疎水性層、及び多孔質支持膜の順に各部材を積層する方法としては公知の方法を採用することができ、例えば、ラミネート法が挙げられる。ラミネート法としては、例えば、ドライラミネート、ホットメルトラミネート等が挙げられる。具体的には、接着剤又は接着フィルムを用いてこれらを貼り合わせる。 In the production process of (3), a known method can be adopted as a method of laminating each member in the order of the hydrophobic layer, the polymer membrane, the hydrophobic layer, and the porous support membrane. Can be mentioned. Examples of the laminating method include dry lamination and hot melt lamination. Specifically, these are bonded together using an adhesive or an adhesive film.
接着剤は特に限定されないが、水系接着剤（例えば、α−オレフィン系接着剤、水性高分子−イソシアネート系接着剤等）、水分散系接着剤（例えば、アクリル樹脂エマルジョン接着剤、エポキシ樹脂エマルジョン接着剤、酢酸ビニル樹脂エマルジョン接着剤等）、溶剤系接着剤（例えば、ニトロセルロース接着剤、塩化ビニル樹脂溶剤系接着剤、クロロプレンゴム系接着剤等）、反応系接着剤（例えば、シアノアクリレート系接着剤、アクリル樹脂系接着剤、シリコーン系接着剤等）、ホットメルト接着剤（例えば、エチレン−酢酸ビニル樹脂ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリアミド樹脂ホットメルト接着剤、ポリオレフィン樹脂ホットメルト接着剤等）等が挙げられる。接着フィルムとしては、ポリビニルブチラール、ポリウレタン、エチレン−酢酸ビニル共重合体樹脂等の熱可塑性透明樹脂からなるフィルム等が挙げられる。高分子膜及び多孔質支持膜のガス透過性を妨げない範囲であれば、接着剤又は接着フィルムの層の厚さは特に限定されない。 Adhesives are not particularly limited, but water-based adhesives (for example, α-olefin-based adhesives, aqueous polymer-isocyanate-based adhesives, etc.), water-dispersed adhesives (for example, acrylic resin emulsion adhesives, epoxy resin emulsion adhesives) Adhesives, vinyl acetate resin emulsion adhesives), solvent-based adhesives (eg, nitrocellulose adhesives, vinyl chloride resin solvent-based adhesives, chloroprene rubber adhesives, etc.), reactive adhesives (eg, cyanoacrylate adhesives) Adhesive, acrylic resin adhesive, silicone adhesive, etc.), hot melt adhesive (for example, ethylene-vinyl acetate resin hot melt adhesive, polyamide resin hot melt adhesive, polyamide resin hot melt adhesive, polyolefin resin hot melt) Adhesive etc.). Examples of the adhesive film include films made of a thermoplastic transparent resin such as polyvinyl butyral, polyurethane, and ethylene-vinyl acetate copolymer resin. The thickness of the layer of the adhesive or adhesive film is not particularly limited as long as it does not interfere with the gas permeability of the polymer membrane and the porous support membrane.
本発明の複合分離膜の製造方法の第二態様としては、（１）多孔質支持膜上に疎水性ポリマーを含む有機溶液を塗布し、有機溶媒を除去して疎水性ポリマーを硬化させて疎水性層を多孔質支持膜上に形成する工程、（２）多孔質支持膜上に形成した疎水性層上に、前記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミン基を有するアミン化合物及び多官能重合性単量体を含むモノマー溶液、又は前記アミン化合物、ポリビニルアルコール、及び架橋剤を含む混合溶液を塗布し、あるいは疎水性層を有する多孔質支持膜を前記モノマー溶液又は前記混合溶液に浸漬し、前記多官能重合性単量体を重合反応又はポリビニルアルコールを架橋させることにより、生成する高分子重合体内に前記アミン化合物が固定化されてなる高分子膜を疎水性層上に形成する工程、及び（３）高分子膜上に疎水性ポリマーを含む有機溶液を塗布し、有機溶媒を除去して疎水性ポリマーを硬化させて疎水性層を高分子膜上に形成する工程を含む方法が挙げられる。 As a second embodiment of the method for producing a composite separation membrane of the present invention, (1) an organic solution containing a hydrophobic polymer is applied onto a porous support membrane, the organic solvent is removed, and the hydrophobic polymer is cured to make the hydrophobic (2) an amine compound having an amidoamine group represented by the formula [I] and / or [II] on the hydrophobic layer formed on the porous support membrane; And a monomer solution containing a polyfunctional polymerizable monomer, or a mixed solution containing the amine compound, polyvinyl alcohol, and a crosslinking agent, or a porous support membrane having a hydrophobic layer is used as the monomer solution or the mixed solution. The polymer film formed by immobilizing the amine compound in the polymer polymer produced by immersing the polyfunctional polymerizable monomer in the polymerization reaction or cross-linking polyvinyl alcohol to form a hydrophobic layer And (3) a step of applying an organic solution containing a hydrophobic polymer on the polymer film, removing the organic solvent to cure the hydrophobic polymer, and forming a hydrophobic layer on the polymer film The method containing is mentioned.
（２）の製造工程において、前記アミン化合物及び多官能重合性単量体を含むモノマー溶液は、前記アミン化合物及び多官能重合性単量体を溶媒に溶解させて調製する。 In the production process (2), the monomer solution containing the amine compound and the polyfunctional polymerizable monomer is prepared by dissolving the amine compound and the polyfunctional polymerizable monomer in a solvent.
溶媒は特に限定されず、重合反応を阻害しない溶媒であれば公知のものを広く使用できる。このような溶媒としては、例えば、メタノール、エタノール、２−プロパノール、テトラヒドロフラン、１，４−ジオキサン等が挙げられる。これらの溶媒には水が含まれていてもよい。 A solvent is not specifically limited, A well-known thing can be widely used if it is a solvent which does not inhibit a polymerization reaction. Examples of such a solvent include methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane and the like. These solvents may contain water.
モノマー溶液には、通常、上記した重合開始剤が添加される。光重合を行う場合は、上記した増感剤を添加することができる。熱重合開始剤、光重合開始剤、及び増感剤の使用量は上記と同様である。 The above-mentioned polymerization initiator is usually added to the monomer solution. When carrying out photopolymerization, the above-described sensitizer can be added. The usage-amount of a thermal-polymerization initiator, a photoinitiator, and a sensitizer is the same as the above.
塗布又は浸漬の方法は特に限定されないが、公知のスピンコーティング法又はディップコーティング法が好ましい。 Although the method of application | coating or immersion is not specifically limited, The well-known spin coating method or the dip coating method is preferable.
スピンコーティング法は、疎水性層を回転させながら、その表面にモノマー溶液又は混合溶液を所定量滴下し、モノマー溶液又は混合溶液を均一塗布する方法である。スピンコーティングにおけるモノマー溶液又は混合溶液の滴下量は、０．１〜１μｌ／ｍｍ２程度であることが好ましい。スピンコーティングにおける回転速度は、５００〜４０００ｒｐｍ程度であることが好ましい。 The spin coating method is a method in which a predetermined amount of a monomer solution or a mixed solution is dropped on the surface of a hydrophobic layer while rotating the hydrophobic layer, and the monomer solution or the mixed solution is uniformly applied. The dropping amount of the monomer solution or mixed solution in spin coating is preferably about 0.1 to 1 μl / mm 2 . The rotation speed in spin coating is preferably about 500 to 4000 rpm.
ディップコーティング法は、モノマー溶液又は混合溶液中に疎水性層を有する多孔質支持膜を浸し、ついで１〜１０ｍｍ／ｓｅｃ程度で引き上げることにより、疎水性層上にモノマー溶液又は混合溶液を塗布する方法である。 The dip coating method is a method of applying a monomer solution or a mixed solution on a hydrophobic layer by immersing a porous support membrane having a hydrophobic layer in a monomer solution or a mixed solution and then pulling it up at about 1 to 10 mm / sec. It is.
第二態様の複合分離膜の製造方法によると、各部材を接着剤等を介することなく直接積層することができるため、密着性の高い複合分離膜を製造することができる。また、接着剤等を用いていないので、ガス透過性能に優れる複合分離膜を製造することができる。 According to the method for producing a composite separation membrane of the second aspect, since each member can be directly laminated without using an adhesive or the like, a composite separation membrane with high adhesion can be produced. Moreover, since no adhesive or the like is used, a composite separation membrane having excellent gas permeation performance can be produced.
本発明の二酸化炭素の分離方法は、二酸化炭素を含む混合ガスを、前記複合分離膜に接触させて、該混合ガス中の二酸化炭素を選択的に透過させる工程を含む。 The carbon dioxide separation method of the present invention includes a step of bringing a mixed gas containing carbon dioxide into contact with the composite separation membrane to selectively permeate carbon dioxide in the mixed gas.
前記分離方法においては、複合分離膜のガス供給側とガス透過側との間に圧力差を設けておくことが好ましい。圧力差は、通常、ガス透過側を減圧にすることにより設けられる。また、前記分離方法は、通常５〜８０℃、好ましくは室温〜５０℃の温度条件下で行うことが好ましい。 In the separation method, it is preferable to provide a pressure difference between the gas supply side and the gas permeation side of the composite separation membrane. The pressure difference is usually provided by reducing the pressure on the gas permeation side. The separation method is usually carried out at a temperature of 5 to 80 ° C., preferably room temperature to 50 ° C.
混合ガスは、少なくとも二酸化炭素を含むガスであれば特に制限されないが、二酸化炭素と他のガスとの分離性能を向上させるためには、混合ガスの相対湿度を３０％以上に調整しておくことが好ましく、より好ましくは６０〜１００％である。 The mixed gas is not particularly limited as long as it contains at least carbon dioxide, but in order to improve the separation performance between carbon dioxide and other gases, the relative humidity of the mixed gas should be adjusted to 30% or more. Is more preferable, and 60 to 100% is more preferable.
前記分離方法は、例えば、火力発電所、鉄鋼プラント等で発生する燃焼排ガスから二酸化炭素（ＣＯ２）を分離する際に好適に用いられる。 The separation method is preferably used when carbon dioxide (CO 2 ) is separated from combustion exhaust gas generated in, for example, a thermal power plant or a steel plant.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
（多孔質支持膜の作製）
ポリスルホン（Solvay Advanced Polymers Co.、商品名：Udel P-3500）５４ｇをＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）２４６ｇに溶解させてポリスルホン溶液を得た。ポリスルホン溶液を、ガラス板上に固定したＰＥＴ不織布上にアプリケータ（ギャップ２５０μｍ）を用いて塗布し、その後、当該ガラス板を水中に浸漬してポリスルホンを凝固させた。さらに、流水中で約１時間洗浄して溶媒であるＤＭＦを抽出した。その後、室温で１２時間乾燥させて、ＰＥＴ不織布上にポリスルホン多孔層を有する多孔性支持膜を作製した。
Example 1
(Preparation of porous support membrane)
54 g of polysulfone (Solvay Advanced Polymers Co., trade name: Udel P-3500) was dissolved in 246 g of N, N-dimethylformamide (DMF) to obtain a polysulfone solution. The polysulfone solution was applied onto a PET nonwoven fabric fixed on a glass plate using an applicator (gap 250 μm), and then the glass plate was immersed in water to solidify the polysulfone. Furthermore, it wash | cleaned in flowing water for about 1 hour, and DMF which is a solvent was extracted. Then, it was made to dry at room temperature for 12 hours, and the porous support membrane which has a polysulfone porous layer on PET nonwoven fabric was produced.
（複合分離膜の作製）
２成分型シリコーンエラストマー（モメンティブパフォーマンスマテリアルズ社製、商品名：RTV-615、Ａ液及びＢ液）を重量比１０：１（Ａ液：Ｂ液）で混合し、さらにヘキサンで希釈してエラストマー溶液（シリコーン濃度３重量％）を調製した。
作製した多孔性支持膜上に、調製したエラストマー溶液をアプリケータ（ギャップ１００μｍ）を用いて塗布し、１３０℃のオーブン中で１０分間キュアしてシリコーンエラストマーを硬化させて、多孔性支持膜上に疎水性層（厚み１μｍ）を形成した。
下記式で示される第０世代ポリアミドアミンデンドリマーを５０重量％含むメタノール溶液（アルドリッチ社製）を４０℃の水浴中にてロータリーエバポレータを用いて５時間減圧蒸留し、一晩真空乾燥してポリアミドアミンデンドリマーのみを単離した。
ポリビニルアルコール（和光純薬工業社製、重合度：２０００、ケン化度：９８％以上）５ｇを９５ｇの純水に溶解させてポリビニルアルコール溶液（ポリビニルアルコール濃度５重量％）を調製した。
単離したポリアミドアミンデンドリマー３ｇ、調製したポリビニルアルコール溶液４０ｇ、及びジイソプロポキシ（ビストリエタノールアミネート）チタンを８０重量％含むイソプロパノール溶液（マツモトファインケミカル社製、オルガチックスＴＣ−４００）０．１２５ｇを混合して混合溶液を調製した。
多孔性支持膜上に形成した疎水性層上に、調製した前記混合溶液をアプリケータ（ギャップ１５００μｍ）を用いて塗布し、１日自然乾燥させた。その後、１２０℃で１時間熱処理を行い、疎水性層上に高分子膜（厚み１５０μｍ）を形成した。
その後、高分子膜上に、前記エラストマー溶液をアプリケータ（ギャップ１００μｍ）を用いて塗布し、１３０℃のオーブン中で１０分間キュアしてシリコーンエラストマーを硬化させて、高分子膜上に疎水性層（厚み１μｍ）を形成して複合分離膜を作製した。
(Production of composite separation membrane)
Two-component silicone elastomer (Momentive Performance Materials, trade name: RTV-615, liquid A and liquid B) is mixed at a weight ratio of 10: 1 (liquid A: liquid B), and further diluted with hexane to give an elastomer. A solution (silicone concentration 3% by weight) was prepared.
The prepared elastomer solution is applied onto the prepared porous support membrane using an applicator (gap 100 μm), cured in an oven at 130 ° C. for 10 minutes to cure the silicone elastomer, and then applied onto the porous support membrane. A hydrophobic layer (thickness 1 μm) was formed.
A methanol solution containing 50% by weight of the 0th generation polyamidoamine dendrimer represented by the following formula (Aldrich) was distilled under reduced pressure for 5 hours in a water bath at 40 ° C. using a rotary evaporator and vacuum dried overnight to polyamidoamine. Only the dendrimer was isolated.
5 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, polymerization degree: 2000, saponification degree: 98% or more) was dissolved in 95 g of pure water to prepare a polyvinyl alcohol solution (polyvinyl alcohol concentration 5% by weight).
3 g of the isolated polyamidoamine dendrimer, 40 g of the prepared polyvinyl alcohol solution, and 0.125 g of an isopropanol solution containing 80% by weight of diisopropoxy (bistriethanolamate) titanium (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS TC-400) are mixed. Thus, a mixed solution was prepared.
On the hydrophobic layer formed on the porous support membrane, the prepared mixed solution was applied using an applicator (gap 1500 μm) and naturally dried for one day. Thereafter, heat treatment was performed at 120 ° C. for 1 hour to form a polymer film (thickness 150 μm) on the hydrophobic layer.
Thereafter, the elastomer solution is applied onto the polymer film using an applicator (gap 100 μm), cured in an oven at 130 ° C. for 10 minutes to cure the silicone elastomer, and the hydrophobic layer is formed on the polymer film. (Thickness 1 μm) was formed to prepare a composite separation membrane.
比較例１
実施例１において、高分子膜の両面に疎水性層を設けなかった以外は実施例１と同様の方法で複合分離膜を作製した。
Comparative Example 1
In Example 1, a composite separation membrane was produced in the same manner as in Example 1 except that the hydrophobic layers were not provided on both sides of the polymer membrane.
〔測定及び評価方法〕
（分離係数α、パーミアンス（透過率）ＱＣＯ２及びＱＨｅの測定）
ガス透過測定装置（ジーエルサイエンス株式会社製）を用いた。複合分離膜の供給側にＣＯ２ガス（８０体積％）及びＨｅガス（２０体積％）を含む混合ガスを大気圧下で供給し、透過側には大気圧の乾燥させたＡｒガスを流通させた。なお、混合ガスはバブラーを用いて８０％に加湿した。透過側のＡｒガスの一部を所定時間の間隔でガスクロマトグラフに導入してＣＯ２ガス及びＨｅガスの濃度変化を測定した。時間経過に対するＣＯ２ガス及びＨｅガスの濃度の増加量からＣＯ２ガス及びＨｅガスのパーミアンスを求めた。混合ガスを供給して３０分毎に１５時間測定し、性能（数値）が安定したときの数値を採用した。
ガス透過測定装置の設定条件、ガスクロマトグラフィーの分析条件、ガスのパーミアンスの算出方法は以下のとおりである。
[Measurement and evaluation method]
(Measurement of separation factor α, permeance (transmittance) Q CO2 and Q He )
A gas permeation measuring device (manufactured by GL Sciences Inc.) was used. A mixed gas containing CO 2 gas (80% by volume) and He gas (20% by volume) is supplied to the supply side of the composite separation membrane at atmospheric pressure, and dried Ar gas at atmospheric pressure is circulated to the permeation side. It was. The mixed gas was humidified to 80% using a bubbler. A part of the Ar gas on the permeate side was introduced into the gas chromatograph at predetermined time intervals to measure changes in the concentration of CO 2 gas and He gas. It was determined permeance of CO 2 gas and He gas from the increase in the concentration of CO 2 gas and He gas with respect to time. The mixed gas was supplied and measured every 30 minutes for 15 hours, and the value when the performance (numerical value) was stabilized was adopted.
The setting conditions of the gas permeation measuring device, the analysis conditions of the gas chromatography, and the calculation method of the gas permeance are as follows.
<ガス透過測定装置の設定条件>
供給ガス量：１００ｃｃ／ｍｉｎ
供給ガス組成：ＣＯ２ガス（８０体積％）、Ｈｅガス（２０体積％）
透過側流量ガス：Ａｒガス
透過側流量ガス量：１０ｃｃ／ｍｉｎ
透過面積：８．０４ｃｍ２
測定温度：４０℃
バブラー温度：３５．９℃
<Setting conditions of gas permeation measuring device>
Supply gas amount: 100cc / min
Supply gas composition: CO 2 gas (80% by volume), He gas (20% by volume)
Permeation side flow rate gas: Ar gas transmission side flow rate gas amount: 10 cc / min
Transmission area: 8.04 cm 2
Measurement temperature: 40 ° C
Bubbler temperature: 35.9 ° C
<ガスクロマトグラフィーの分析条件>
Ａｒキャリアーガス量：１０ｃｃ／ｍｉｎ
ＴＣＤ温度：１５０℃
オーブン温度：８０℃
ＴＣＤ電流：７０ｍＡ
ＴＣＤ極性：[−]ＬＯＷ
ＴＣＤ ＬＯＯＰ：１ｍｌ シリコスチール管 １／１６”×１．０×６５０ｍｍ
<Analysis conditions for gas chromatography>
Ar carrier gas amount: 10cc / min
TCD temperature: 150 ° C
Oven temperature: 80 ° C
TCD current: 70 mA
TCD polarity: [-] LOW
TCD LOOP: 1ml silico steel tube 1/16 "x 1.0 x 650mm
<分離係数α、パーミアンスＱＣＯ２及びＱＨｅの算出方法>
ガスクロマトグラフィーで求めた透過側流量ガス中のガス濃度からガスの透過量Ｎを算出して、下記式１及び２によりパーミアンスＱＣＯ２及びＱＨｅを計算した。また、下記式３により分離係数αを計算した。
The gas permeation amount N was calculated from the gas concentration in the permeation side flow rate gas determined by gas chromatography, and permeances Q CO2 and Q He were calculated by the following equations 1 and 2. Further, the separation factor α was calculated by the following formula 3.
（耐水性評価）
作製した複合分離膜を２４時間純水中に浸漬し、その後、上記と同様の方法で分離係数α、パーミアンスＱＣＯ２及びＱＨｅを測定した。
(Water resistance evaluation)
The produced composite separation membrane was immersed in pure water for 24 hours, and then the separation factor α, permeance Q CO2 and Q He were measured by the same method as described above.
表２から、実施例１の複合分離膜は、疎水性層が設けられているため、高分子膜からのアミン化合物の溶出が防止され、２４時間純水中に浸漬した場合であっても分離性能の低下が抑制されていることがわかる。一方、比較例１の複合分離膜は、疎水性層が設けられておらず、高分子膜が露出しているため、結露水によって高分子膜からアミン化合物が溶出していると考えられる。特に、比較例１の複合分離膜を２４時間純水中に浸漬した場合には、高分子膜からのアミン化合物の溶出により分離性能の低下が著しい。 From Table 2, since the composite separation membrane of Example 1 is provided with a hydrophobic layer, elution of the amine compound from the polymer membrane is prevented, and separation is performed even when immersed in pure water for 24 hours. It can be seen that the decrease in performance is suppressed. On the other hand, since the composite separation membrane of Comparative Example 1 is not provided with a hydrophobic layer and the polymer membrane is exposed, it is considered that the amine compound is eluted from the polymer membrane by the condensed water. In particular, when the composite separation membrane of Comparative Example 1 is immersed in pure water for 24 hours, the separation performance is remarkably lowered due to elution of the amine compound from the polymer membrane.
本発明の複合分離膜は、二酸化炭素を他のガスから分離するために用いられ、例えば、火力発電所、鉄鋼プラント等で発生する燃焼排ガスから二酸化炭素を分離する際に好適に用いられる。
The composite separation membrane of the present invention is used for separating carbon dioxide from other gases. For example, it is suitably used for separating carbon dioxide from combustion exhaust gas generated in a thermal power plant, a steel plant, or the like.
Claims (4)
前記アミン化合物は、下記式［Ｉ］及び／又は［ＩＩ］で示されるアミドアミノ基を有しており、かつ前記高分子膜の両面に疎水性層が積層されていることを特徴とする複合分離膜。
（式中、Ａ１は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。）
（式中、Ａ２は炭素数１〜３の二価有機残基を示し、ｎは０または１の整数を示す。） In a composite separation membrane in which a polymer membrane containing a polymer and an amine compound and a porous support membrane are laminated,
The amine compound has an amidoamino group represented by the following formula [I] and / or [II], and a hydrophobic layer is laminated on both surfaces of the polymer membrane. film.
(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1.)
A method for separating carbon dioxide, comprising the step of bringing a mixed gas containing carbon dioxide into contact with the composite separation membrane according to any one of claims 1 to 3 to selectively permeate carbon dioxide in the mixed gas.
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